KR20220152653A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic light emitting compound and an organic light emitting device including the same, wherein the novel organic light emitting compound represented by chemical formula I is used as a hole transport material in an organic layer of an organic light emitting device, or is used in a light efficiency improvement layer provided in the organic light emitting device, thereby realizing light emitting characteristics such as low voltage driving of a device, excellent color purity and luminous efficiency.

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound, and more particularly, is employed as a light efficiency improvement layer (capping layer) material provided in an organic light emitting device or as a hole transport material in an organic layer such as a hole transport layer in an organic light emitting device. It relates to an organic light emitting compound that employs the organic light emitting compound and an organic light emitting device having remarkably improved light emitting characteristics such as low voltage driving of the device and excellent light emitting efficiency.

Organic light emitting devices can not only be formed on a transparent substrate, but also can be driven at a low voltage of 10 V or less compared to plasma display panels or inorganic electroluminescent (EL) displays, and consume relatively little power. , It has the advantage of being excellent in color, and can show three colors of green, blue, and red, so it has recently become a subject of much interest as a next-generation display device.

However, in order for the organic light emitting device to exhibit the above characteristics, the materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, and electron injection materials, are supported by stable and efficient materials. However, the development of stable and efficient organic layer materials for organic light emitting devices has not yet been sufficiently accomplished.

Therefore, in order to implement a more stable organic light emitting device, and to achieve high efficiency, long lifespan, and large size of the device, further improvement in terms of efficiency and lifespan characteristics is required, and in particular, development of materials forming each organic layer of the organic light emitting device is required. It is desperately needed.

In this regard, studies have recently been actively conducted to improve the mobility of existing organic materials for the hole transport layer material in the structure of the organic light emitting device.

In addition, recently, research on improving the characteristics of an organic light emitting device by changing the performance of each organic layer material, as well as technology for improving color purity and increasing luminous efficiency by optimizing optical thickness between an anode and a cathode, has been conducted. It is considered as one of the important factors to improve performance, and as an example of this method, a capping layer is used on an electrode to increase light efficiency and achieve excellent color purity.

Therefore, the present invention is employed in a light efficiency improving layer provided in an organic light emitting device or employed in an organic layer such as a hole transport layer in an organic light emitting device to realize excellent light emitting characteristics such as low voltage driving of the device and improved light emitting efficiency. It is intended to provide a light emitting compound and an organic light emitting device including the same.

In order to solve the above problems, the present invention provides any one organic light emitting compound selected from compounds represented by the following [Chemical Formula I].

[Formula I]

The characteristic structure of [Chemical Formula 1] and specific compounds implemented thereby, X, Y, L, Ar ₁ to Ar ₃ will be described later.

In addition, the present invention is an organic light emitting device including a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein the hole transport layer in the organic light emitting device contains the [Formula I] It provides an organic light emitting device comprising a compound represented by

In addition, a light efficiency improvement layer (Capping layer) formed on at least one side opposite to the organic layer among the upper or lower portions of the first electrode and the second electrode is further included, and the light efficiency improvement layer is represented by the [Formula I] An organic light emitting device comprising an organic light emitting compound is provided.

When the organic light emitting compound according to the present invention is used as a hole transport material in a light efficiency improving layer provided in an organic light emitting device and an organic layer in an organic light emitting device, it can realize improved light emitting characteristics such as low voltage driving of the device, excellent light emitting efficiency, and color purity. It can be usefully used in various display devices.

Hereinafter, the present invention will be described in more detail.

The present invention is employed as a light efficiency improving layer provided in an organic light emitting device or a material for a hole transport layer in an organic light emitting device, and is represented by the following [Formula I] capable of achieving low voltage driving of the device and luminous properties such as excellent luminous efficiency and color purity. It relates to an organic luminescent compound characterized in that it becomes.

[Formula I]

In the above [Formula I],

X and Y are the same as or different from each other, and are each independently O, S or NR.

Wherein R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated group having 1 to 20 carbon atoms Alkyl group, substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms and substituted or unsubstituted 2 carbon atoms to 30 heteroaryl groups.

According to one embodiment of the present invention, the skeleton structure of [Formula I] may be the following structure, wherein X is O, S or NR as described above (the definition of R is the same).

[Formula Ⅰ-1] [Formula Ⅰ-2]

L is selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, n is an integer of 1 to 3, respectively, and when n is 2 or more, a plurality The two L's are the same as or different from each other.

Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and o and p are each It is an integer of 1 to 3, and when o and p are 2 or more, respectively, a plurality of Ar ₁ to Ar ₂ are the same as or different from each other.

Ar ₃ is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

Meanwhile, in the definition of R, L, and Ar ₁ to Ar ₃ , 'substituted or unsubstituted' means that each of R, L, and Ar ₁ to Ar ₃ is deuterium, a halogen group, a cyano group, a nitro group, Hydroxy group, silyl group, alkyl group, amine group, halogenated alkyl group, deuterated alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, aryl group, heteroaryl group, alkylsilyl group and arylsilyl groups, substituted with one or two or more substituents selected from the group consisting of two or more substituents among the substituents connected to each other, or without any substituents.

For example, a substituted aryl group refers to a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. means it has been

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group, and condensed heterocyclic groups thereof, such as a benzquinoline group. , It means that a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, etc. are substituted with the above substituents.

In the present invention, examples of the substituents will be described in detail below, but are not limited thereto.

In the present invention, the alkyl group may be a straight chain or branched chain, and specific examples include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group , sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentyl group methyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

In the present invention, the alkoxy group may be straight chain or branched chain. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , benzyloxy group, p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, the alkyl group or alkoxy group may be a deuterated alkyl group or alkoxy group, a halogenated alkyl group, or an alkoxy group substituted with deuterium or a halogen group.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30, and also includes a polycyclic aryl group structure in which cycloalkyl or the like is fused, and a monocyclic aryl group Examples of include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and the like, and examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a tetracenyl group, and a chrysenyl group. , fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited only to these examples.

,

,

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are linked through one atom, for example

,

,

etc.

,

등이 있다.In the present invention, the fluorenyl group includes the structure of an open fluorenyl group, where the open fluorenyl group is a structure in which one ring compound is disconnected from a structure in which two ring organic compounds are connected through one atom. , for example

,

etc.

,

,

,

등이 있다.In addition, the carbon atom of the ring may be substituted with any one or more heteroatoms selected from N, S and O, for example

,

,

,

etc.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably has 3 to 30 carbon atoms, and is a polycyclic group in which cycloalkyl or heterocycloalkyl is fused. It includes a heteroaryl group structure, and specific examples thereof in the present invention include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, and a bipyridyl group. , pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenoxazine group, phenothiazine group, etc., but only these It is not limited.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, a heteroarylamine group, an arylheteroarylamine group, and the like, and the aryl (heteroaryl)amine group is substituted with an aryl group and/or a heteroaryl group. It means an amine, and the alkylamine group means an amine substituted with an alkyl, and examples of the aryl (heteroaryl) amine group include a substituted or unsubstituted mono aryl (heteroaryl) amine group, a substituted or unsubstituted diaryl ( There is a heteroaryl) amine group or a substituted or unsubstituted triaryl (heteroaryl) amine group, and the aryl group and the heteroaryl group in the aryl (heteroaryl) amine group are the same as the definitions of the aryl group and the heteroaryl group, and the above The alkyl group of the alkylamine group is also the same as the definition of the above alkyl group.

Illustratively, the arylamine group includes a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenyl group. amine group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolylamine group, phenyltolylamine group and triphenylamine group, but are not limited thereto.

In the present invention, the silyl group is an unsubstituted silyl group or an alkylsilyl group or an arylsilyl group substituted with an alkyl group or an aryl group, and specific examples of such a silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, and trimethylsilyl. and the like, but are not limited thereto.

Specific examples of the substituent halogen group used in the present invention include fluorine (F), chlorine (Cl), and bromine (Br).

In the present invention, the cycloalkyl group refers to and includes monocyclic, polycyclic and spiroalkyl radicals, preferably containing ring carbon atoms of 3 to 20 carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo heptyl, spirodecyl, spirundecyl, adamantyl, and the like, and the cycloalkyl group may be optionally substituted.

In the present invention, heterocycloalkyl groups refer to and include aromatic and non-aromatic cyclic radicals containing one or more heteroatoms, one or more heteroatoms being O, S, N, P, B, Si, and Se , Preferably selected from O, N or S, specifically, when N is included, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, and the like.

The organic light emitting compound according to the present invention represented by [Formula I] can be used as various organic layers such as a hole transport layer in an organic light emitting device due to its structural specificity, and can also be used as a material for a light efficiency improvement layer provided in an organic light emitting device. have.

Preferred specific examples of the organic light-emitting compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited thereto.

As described above, the organic light emitting compound according to the present invention can synthesize organic light emitting compounds having various properties by using a characteristic skeleton exhibiting unique properties and a moiety having unique properties introduced thereto, As a result, when the organic light emitting compound according to the present invention is applied to various organic layer materials such as a hole transport layer and when applied to a light efficiency improvement layer provided in an organic light emitting device, the light emitting characteristics such as light emitting efficiency of the device can be further improved. can

In addition, the compound of the present invention can be applied to a device according to a general organic light emitting device manufacturing method.

An organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic layer disposed therebetween, and the organic light emitting compound according to the present invention is used in the organic layer of the device. Except for this, it can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a light efficiency improvement layer (capping layer), and the like. However, it is not limited thereto and may include fewer or more organic layers.

In addition, the organic light emitting device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic layer, a second electrode (cathode) and a light efficiency improvement layer, wherein the light efficiency improvement layer is under the first electrode ( bottom emission) or on top of the second electrode (top emission).

In the method formed on the second electrode (top emission), the light formed in the light emitting layer is emitted toward the cathode, and the light emitted toward the cathode passes through the light efficiency improving layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. The wavelength of is amplified and thus the light efficiency is increased. In addition, the light efficiency of the organic electric element is improved by employing the compound according to the present invention in the light efficiency improvement layer according to the same principle as the method formed on the bottom emission of the first electrode. .

An organic layer structure of a preferred organic light emitting device according to the present invention will be described in more detail in Examples to be described later.

In addition, the organic light emitting device according to the present invention uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof on a substrate. It can be manufactured by depositing an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer can be formed by using various polymer materials and using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. Can be made in layers.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , but conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof, and multilayers such as LiF/Al or LiO ₂ /Al. structural materials, etc., but are not limited thereto.

The hole injection material is a material capable of receiving holes from the anode at a low voltage, and preferably has a highest occupied molecular orbital (HOMO) between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high hole mobility is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts. can be further improved.

The light-emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazoles, benzthiazoles, and Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited thereto.

As the electron transport material, a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex, but are not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

In addition, the organic light emitting compound according to the present invention may act in organic electronic devices including organic solar cells, organic photoreceptors, organic transistors, and the like, on a principle similar to that applied to organic light emitting devices.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

synthesis example 1: Synthesis of Compound 1

(One) manufacturing example 1: synthesis of intermediate 1-1

B-(2-Phenyl-7-benzoxazolyl)boronic acid (10.0 g, 0.042 mol), 2-Bromonitrobenzene (10.1 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to (1.0 g, 0.001 mol), followed by stirring at 100 °C for 6 hours. After completion of the reaction, 9.8 g (yield 72.6%) of <Intermediate 1-1> was obtained by extraction, concentration, and column.

(2) manufacturing example 2: Synthesis of Intermediate 1-2

Intermediate 1-1 (10.0 g, 0.032 mol), PPh ₃ (20.7 g, 0.079 mol), and 200 mL of dichlorobenzene were added thereto, followed by stirring under reflux at 180 °C for 5 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 6.2 g of <Intermediate 1-2> (yield: 69.0%).

(3) manufacturing example 3: synthesis of intermediates 1-3

155 mL of DMF was added to Intermediate 1-2 (10.0 g, 0.035 mol), 1-Fluoro-4-iodobenzene (9.4 g, 0.042 mol), and Cs ₂ CO ₃ (7.3 g, 0.053 mol) and incubated at 150 °C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, 11.5 g (yield 67.2%) of <Intermediate 1-3> was obtained by extraction, concentration, column and recrystallization.

(4) manufacturing example 4: Synthesis of Compound 1

Intermediate 1-3 (10.0 g, 0.021 mol), Bis(4-biphenylyl)amine (9.9 g, 0.031 mol), NaOtBu (4.0 g, 0.041 mol), Pd(dba) ₂ (0.6 g, 0.001 mol), t Toluene 150 mL was added to -Bu ₃ P (0.4 g, 0.002 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, 9.2 g (yield: 65.8%) of <Compound 1> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=679 [(M+1) ⁺ ]

synthesis example 2: synthesis of compound 20

(One) manufacturing example 1: synthesis of compound 20

Intermediate 1-3 (10.0 g, 0.021 mol), Bis(dibenzofuran-3-yl)amine (10.8 g, 0.031 mol), NaOtBu (4.0 g, 0.041 mol), Pd(dba) ₂ (0.6 g, 0.001 mol) , Toluene 150 mL was added to t-Bu ₃ P (0.4 g, 0.002 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, after extraction and concentration, 8.9 g of <Compound 20> was obtained by column and recrystallization (yield: 61.2%).

LC/MS: m/z=707 [(M+1) ⁺ ]

synthesis example 3: synthesis of compound 43

(One) manufacturing example 1: synthesis of intermediate 43-1

155 mL of DMF was added to Intermediate 1-2 (10.0 g, 0.035 mol), 1-Fluoro-4-(4-iodophenyl)benzene (12.6 g, 0.042 mol), and Cs ₂ CO ₃ (7.3 g, 0.053 mol). It was reacted by stirring under reflux at 150 °C for 1 hour. After completion of the reaction, 12.8 g (yield: 64.7%) of <Intermediate 43-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 43

Intermediate 43-1 (10.0 g, 0.018 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (9.0 g, 0.027 mol), NaOtBu (3.4 g, 0.036 mol), Pd (dba ) ₂ (0.5 g, 0.001 mol) and t-Bu ₃ P (0.4 g, 0.002 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 8.5 g (yield: 62.1%) of <Compound 43> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=769 [(M+1) ⁺ ]

synthesis example 4: synthesis of compound 53

(One) manufacturing example 1: synthesis of intermediate 53-1

2-Bromo-9-spirobifluorene (10.0 g, 0.025 mol), 2-Amino-9,9-dimethylfluorene (7.9 g, 0.038 mol), NaOtBu (4.9 g, 0.051 mol), Pd(dba) ₂ (0.7 g, 0.001 mol) and t-Bu ₃ P (0.5 g, 0.003 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 7.4 g (yield: 55.9%) of <Intermediate 53-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: synthesis of compound 53

Intermediate 43-1 (10.0 g, 0.018 mol), Intermediate 53-1 (13.9 g, 0.027 mol), NaOtBu (3.4 g, 0.036 mol), Pd(dba) ₂ (0.5 g, 0.001 mol), t-Bu ₃ 150 mL of Toluene was added to P (0.4 g, 0.002 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 10.1 g (yield: 59.3%) of <Compound 53> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=957 [(M+1) ⁺ ]

synthesis example 5: Synthesis of Compound 108

(One) manufacturing example 1: synthesis of intermediate 108-1

7-Bromo-2-phenylbenzo[d]thiazole (10.0 g, 0.035 mol), Bis(pinacolato)diboron (10.5 g, 0.041 mol), KOAc (10.2 g, 0.103 mol), Pd(dppf)Cl ₂ (1.3 g , 0.002 mol) into 200 mL of dioxane, followed by stirring at 100 °C for 12 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 8.7 g of <Intermediate 108-1> (yield: 74.9%).

(2) manufacturing example 2: synthesis of intermediate 108-2

Intermediate 108-1 (10.0 g, 0.030 mol), 2-Bromonitrobenzene (7.2 g, 0.036 mol), K ₂ CO ₃ (12.3 g, 0.089 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.001 mol) Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added thereto and reacted by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 7.1 g of <Intermediate 108-2> (yield: 72.0%).

(3) manufacturing example 3: synthesis of intermediate 108-3

Intermediate 108-2 (10.0 g, 0.030 mol), PPh ₃ (19.7 g, 0.075 mol), and 200 mL of dichlorobenzene were added and reacted by stirring at 180 °C for 5 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 6.2 g of <Intermediate 108-3> (yield: 68.6%).

(4) manufacturing example 4: synthesis of intermediate 108-4

155 mL of DMF was added to intermediate 108-3 (10.0 g, 0.033 mol), 1-Fluoro-4-iodobenzene (8.9 g, 0.040 mol), and Cs ₂ CO ₃ (6.9 g, 0.050 mol) at 150 °C for 12 hours. The mixture was reacted by stirring. After completion of the reaction, 10.9 g (yield 65.2%) of <Intermediate 108-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) manufacturing example 5: Synthesis of Compound 108

Intermediate 108-4 (10.0 g, 0.020 mol), 2-Phenyl-N- (4-phenylphenyl)aniline (9.6 g, 0.030 mol), NaOtBu (3.8 g, 0.040 mol), Pd (dba) ₂ (0.6 g, 0.001 mol) and t-Bu ₃ P (0.4 g, 0.002 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, the mixture was extracted and concentrated, followed by column and recrystallization to obtain 8.7 g of <Compound 108> (yield: 62.8%).

LC/MS: m/z=695 [(M+1) ⁺ ]

synthesis example 6: Synthesis of Compound 115

(One) manufacturing example 1: synthesis of intermediate 115-1

3,5-Diphenylaniline (10.0 g, 0.041 mol), 3-Bromodibenzo[b,d]furan (15.1 g, 0.061 mol), NaOtBu (7.8 g, 0.082 mol), Pd(dba) ₂ (1.2 g, 0.002 mol) ), t-Bu ₃ P (0.8 g, 0.004 mol) was added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 9.7 g (yield: 57.8%) of <Intermediate 115-1> was obtained by extraction, concentration, column and recrystallization.

(2) manufacturing example 2: synthesis of compound 115

Intermediate 108-4 (10.0 g, 0.020 mol), Intermediate 115-1 (12.3 g, 0.030 mol), NaOtBu (3.8 g, 0.040 mol), Pd(dba) ₂ (0.6 g, 0.001 mol), t-Bu ₃ 150 mL of Toluene was added to P (0.4 g, 0.002 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 10.5 g (yield: 67.1%) of <Compound 115> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=785 [(M+1) ⁺ ]

synthesis example 7: synthesis of compound 134

(One) manufacturing example 1: synthesis of intermediate 134-1

155 mL of DMF was added to Intermediate 1-2 (10.0 g, 0.035 mol), 1-Fluoro-4-iodonaphthalene (11.5 g, 0.042 mol), and Cs ₂ CO ₃ (7.3 g, 0.053 mol) at 150 °C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, 11.2 g (yield 59.4%) of <Intermediate 134-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: Synthesis of compound 134

Intermediate 134-1 (10.0 g, 0.019 mol), 2-[(Biphenyl-4-yl)amino]-9,9-dimethylfluorene (10.1 g, 0.028 mol), NaOtBu (3.6 g, 0.037 mol), Pd (dba ) ₂ (0.5 g, 0.001 mol) and t-Bu ₃ P (0.4 g, 0.002 mol) were added with 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, 9.8 g (yield: 68.3%) of <Compound 134> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=769 [(M+1) ⁺ ]

synthesis example 8: Synthesis of Compound 174

(One) manufacturing example 1: synthesis of intermediate 174-1

(6-Fluoronaphthalen-2-yl)boronic acid (10.0 g, 0.053 mol), 4-Chloro-1-iodobenzene (15.1 g, 0.063 mol), K ₂ CO ₃ (21.8 g, 0.158 mol), Pd (PPh ₃ ) ₄ (1.2 g, 0.001 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 6.8 g of <Intermediate 174-1> (yield: 50.3%).

(2) manufacturing example 2: synthesis of intermediate 174-2

155 mL of DMF was added to Intermediate 1-2 (10.0 g, 0.035 mol), Intermediate 174-1 (10.8 g, 0.042 mol), and Cs ₂ CO ₃ (7.3 g, 0.053 mol), followed by stirring at 150 °C for 12 hours. made it After completion of the reaction, 11.8 g (yield 64.3%) of <Intermediate 174-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) manufacturing example 3: Synthesis of Compound 174

Intermediate 174-2 (10.0 g, 0.019 mol), Bis(9,9-dimethyl-9H-fluoren-2-yl)amine (11.6 g, 0.029 mol), NaOtBu (3.7 g, 0.038 mol), Pd (dba) ₂ (0.6 g, 0.001 mol) and t-Bu ₃ P (0.4 g, 0.002 mol) were added with 150 mL of Toluene, followed by stirring at 80 °C for 4 hours. After completion of the reaction, the mixture was extracted and concentrated, followed by column and recrystallization to obtain 9.5 g of <Compound 174> (yield: 55.9%).

LC/MS: m/z=885 [(M+1) ⁺ ]

device Example ( HTL )

In an embodiment according to the present invention, the ITO transparent electrode is patterned on a glass substrate of 25 mm × 25 mm × 0.7 mm so that the light emitting area is 2 mm × 2 mm in size by using an ITO glass substrate to which the ITO transparent electrode is attached. After that, it was washed. After the substrate was mounted in a vacuum chamber and the base pressure was 1 × 10 ^-6 torr, an organic material and a metal were deposited on the ITO in the following structure.

device Example 1 to 30

After employing the compound implemented according to the present invention as a hole transport layer and manufacturing an organic light emitting device having the following device structure, emission and driving characteristics of the compound implemented according to the present invention were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (100 nm) / electron blocking layer (EBL1, 10 nm) / light emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was formed on top of the ITO transparent electrode to form a hole injection layer with a thickness of 5 nm, and then the compound according to the present invention described in [Table 1] was formed to a thickness of 100 nm to form a hole transport layer. Thereafter, [EBL1] was deposited to a thickness of 10 nm to form an electron blocking layer, and an emission layer was formed by co-evaporation to a thickness of 20 nm using [BH1] as a host compound and [BD1] as a dopant compound. Thereafter, an electron transport layer (the [ET1] compound Liq 50% doped) was deposited to a thickness of 30 nm, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Thereafter, Al was formed to a thickness of 100 nm to fabricate an organic light emitting device.

device comparative example One

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner as in the device structures of Examples 1 to 30, except that α-NPB was used instead of the compound according to the present invention in the hole transport layer.

Experimental example 1: element Example Luminescence characteristics of 1 to 30

The driving voltage, current efficiency, and color coordinates of the organic light emitting device manufactured according to the above example were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the result values based on 1,000 nit is shown in [Table 1] below.

Example hole transport layer V cd/A CIEx CIEy One Formula 1 4.8 8.1 0.1343 0.1232 2 Formula 5 4.5 8.5 0.1356 0.1197 3 Formula 14 4.6 8.6 0.1359 0.1231 4 Formula 15 4.4 8.4 0.1316 0.1225 5 Formula 18 4.6 8.6 0.1345 0.1261 6 Formula 20 4.4 8.2 0.1331 0.1196 7 Formula 23 4.8 8.4 0.1393 0.1235 8 Formula 24 4.5 8.2 0.1334 0.1163 9 Formula 27 4.7 8.1 0.1353 0.1335 10 Formula 42 4.7 8.5 0.1324 0.1292 11 Formula 43 4.6 8.1 0.1345 0.1328 12 Formula 53 4.5 8.2 0.1339 0.1235 13 Formula 69 4.7 8.5 0.1350 0.1351 14 Formula 75 4.8 8.1 0.1321 0.1340 15 Formula 78 4.7 8.4 0.1326 0.1322 16 Formula 85 4.6 8.3 0.1313 0.1234 17 Formula 102 4.8 8.1 0.1320 0.1244 18 Formula 108 4.7 8.4 0.1345 0.1328 19 Formula 111 4.5 8.2 0.1353 0.1335 20 Formula 115 4.6 8.1 0.1356 0.1301 21 Formula 123 4.5 8.4 0.1321 0.1294 22 Formula 132 4.7 8.2 0.1347 0.1232 23 Formula 134 4.8 8.1 0.1340 0.1192 24 Formula 138 4.4 8.4 0.1312 0.1221 25 Formula 147 4.6 8.5 0.1327 0.1254 26 Formula 166 4.5 8.6 0.1353 0.1293 27 Formula 169 4.8 8.4 0.1359 0.1262 28 Formula 172 4.4 8.2 0.1353 0.1333 29 Formula 173 4.5 8.4 0.1310 0.1266 30 Formula 174 4.6 8.5 0.1376 0.1353 Comparative Example 1 α-NPB 5.1 7.7 0.1332 0.1243

Looking at the results shown in [Table 1], in the case of an organic light emitting device employing the compound according to the present invention in the hole transport layer in the device, the device employing α-NPB used as a conventional hole transport material (Comparative Example 1) In comparison, it can be confirmed that characteristics such as driving voltage and luminous efficiency are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [ET1]

[EBL1]

Claims (8)

An organic light emitting compound represented by the following [Formula I]:
[Formula I]

In the above [Formula I],
X and Y are the same as or different from each other, and are each independently O, S or NR;
Wherein R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated group having 1 to 20 carbon atoms Alkyl group, substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms and substituted or unsubstituted 2 carbon atoms to any one selected from 30 heteroaryl groups;
L is any one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms;
n is each an integer from 1 to 3, and when n is 2 or more, a plurality of L's are the same as or different from each other,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently any one selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
o and p are each an integer of 1 to 3, and when o and p are each 2 or more, a plurality of Ar ₁ to Ar ₂ are the same as or different from each other,
Ar ₃ is any one selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. According to claim 1,
In the definition of R, L, and Ar ₁ to Ar ₃ , 'substituted or unsubstituted' means that each of R, L, and Ar ₁ to Ar ₃ is deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, Silyl group, alkyl group, amine group, halogenated alkyl group, deuterated alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, aryl group, heteroaryl group, alkylsilyl group and aryl An organic light-emitting compound, characterized in that it is substituted with one or two or more substituents selected from the group consisting of silyl groups, is substituted with substituents in which two or more substituents are connected, or does not have any substituents. According to claim 1,
[Formula I] is an organic light-emitting compound, characterized in that selected from the following [Compound 1] to [Compound 189]:

An organic light emitting device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,
At least one of the organic layers includes an organic light emitting compound represented by [Chemical Formula I] according to claim 1. According to claim 4,
The organic layer is selected from a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that simultaneously performs electron transport and electron injection functions, an electron blocking layer, a hole blocking layer, and a light emitting layer. Including one or more floors,
An organic light emitting device, wherein at least one of the layers includes the organic light emitting compound represented by [Chemical Formula I]. According to claim 5,
An organic light emitting device comprising the organic light emitting compound represented by [Chemical Formula 1] in the hole transport layer or the hole injection and hole transport layer at the same time. According to claim 4,
Further comprising a light efficiency improvement layer (Capping layer) formed on at least one side opposite to the organic layer among the upper or lower portions of the first electrode and the second electrode,
The organic light emitting device, characterized in that the light efficiency improving layer comprises an organic light emitting compound represented by the [Chemical Formula I]. According to claim 7,
The organic light emitting device, characterized in that the light efficiency improving layer is formed on at least one of a lower portion of the first electrode or an upper portion of the second electrode.